Process for breaking petroleum emulsions employing gluconic acid salts of oxyalkylated amine-modified thermoplastic phenol-aldehyde resins



ni ted St Melvin De Groote, University City, Mo., assiwor to Petrolite Corporation, Wilmington, Del., a corporation of Delaware No Drawing. Application January 26, 1953, Serial'No. 333,390

a 36 Claims. (Cl.'252341) The present invention is a continuation-in-part of my five co-pending applications, Serial No. 288,746, filed May 19, 1952, now abandoned; Serial No. 296,087, filed June 27, 1952, now U. S. Patent 2,679,488; Serial No. 301,807, filed July 30, 1952, now U. S. Patent 2,743,256; Serial No. 310,555 filed September 19, 1952, now U. S. Patent 2,695,891, and Serial No. 329,486, filed January 2, 1953.

My invention provides an economical and rapid process for resolving petroleum emulsions of the water-inoil type,that are commonly referred to as cut oil, roily oil, emulsified oil, etc., and which comprise fine droplets of naturally-occurring waters orbrines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion.

It also provides an economical and rapid process for separating emulsions which have been prepared under controlled conditions from mineral oil, such as crude oil and relatively soft waters or weak brines. Controlled emulsification and subsequent demulsification under the conditions just mentioned are of significant value in removing impurities, particularly inorganic salts, from pipeline oil.

My aforementioned co-pending application, Serial No. 310,555, filed September 19, 1952, is concerned with a process for breaking petroleum emulsions of the waterin-oil type characterized by subjecting the emulsion to the action of a demulsifier including certain oxyalkylated condensates of cyclic amidines, phenol-aldehyde resins and formaldehyde therein described.

My present invention is concerned with demulsification which involves the use of the aforementioned oxyalkylated amino resin condensate in the form of a gluconic acid salt, i. e., a form in which all or part of the basic nitrogen atoms are neutralized with gluconic acid, i. e., converted into the salt of gluconic acid.

Needless to say, all that is required is to prepare the oxyalkylated amine resin condensates in the manner described in the two aforementioned co-pending applications, and then neutralize with gluconic acid which, for practical purposes is as simple as analogous inorganic reactions.

As far as the use of the herein described products goes for purpose of resolution of petroleum emulsions of the water-in-oil type, I particularly prefer to use the gluconic acid salt of those members which have sufiieient hydrophile character to meet at least the test as set forth in US. Patent No. 2,499,368, dated March 7, 1950, to De Groote et al. In saidpatent such test for emulsification using a water-insoluble solvent, generally xylene, is described as an index of surface activity.

The present invention involves the surface-activity of the gluconic acid salts, i.e., either where only one basic amino nitrogen atom is neutralized or where all basic amino nitrogen atoms are neutralized. Such gluconic acid salts may not necessarily be Xylene-soluble. If such compounds are not Xylene-soluble the obvious chemical equivalent or equivalent chemical test can be made by simply using some suitable solvent, preferably a wateraent ice

' soluble solvent such as ethylene glycol diethylether, or

a low molal alcohol, or a mixture to dissolve the appropriate product being examined and then mix with the equal weight of xylene, followed by addition of water. Such test is obviously the same for the reason that there will be two phases on vigorous shaking and surface activity makes its presence manifest. It is understood the reference in the hereto appended claims as to the use of xylene in the emulsification test includes such obvious variant.

For convenience, what is said hereinafter will be divided into seven parts:

Part 1 is concerned with the general structure of the amine-modified resins which after oxyalkylation are converted to the gluconic acid salt;

Part 2 is concerned with the phenol-aldehyde resin which is subjected to modification by condensation reaction to yield the amine-modified resin;

Part 3 is concerned with suitable basic amidines which may be employed in the preparation of the herein described amine-modified resins;

Part 4 is concernedwith reactions involving the resin, the cyclic amidine, and formaldehyde to produce specific products or compounds which are then subjected to oxyalkylation;

Part 5 is concerned with the oxyalkylation of the prod ucts described in Part 4 preceding;

Part 6 is concerned with the conversion of the basic oxyalkylated derivations described in Part 5, preceding, in the corresponding salt of gluconic acid;

Part 7 is concerned with the resolution of petroleum emulsions of the water-in-oil type by means of the previously described chemical compounds or reaction prodnets in the form of gluconic acid salts.

PART 1 The compounds used in accordance with the presentinvention are the gluconic acid salts of the products obtained by oxyalkylating the amine resin condensates described in applications Serial Nos. 288,746 and 296,087

to which reference is made for a discussion of the general structure of such resins.

These resins may be exemplified by an idealized formula which may, in part, be an over-simplification in an effort to present certain resin structure. Such formula would be the following:

or a substituted tetrahydropyrimidine as previously specified and may be indicated thus:

RI HN in which HN represents a reactive secondary amino group and two occurrences of R represent the remainder of the molecule. Stated another way, what has been depicted in the above formula is an over-simplification as far as the ring compound is concerned which is obvious by reference to a more elaborate formula depicting the actual structure of typical members of the group, such N-CH: CHM) III-CH2 CzH4.NH.CzH4.NH.CmH3u 2-methyl,1-hexadecylaminoethylaminoethylimidazoline there may be a counterbalancing hydrophobe effect or 7 one in which the hydrophobe effect more than counterbalances the hydrophile effect of the nitrogen atom. Finally, in such cases where R contains one or more oxygen atoms, another etfect is introduced, particularly another hydrophile effect. In such instances where there are hydroxyl groups present, needless to say there is a further hydrophile effect introduced. I

The resins employed as raw materials in the instant procedure are characterized by the presence of an aliphatic radical in the ortho or para position, i.e., the phenols themselves are difunctional phenols.

The resins herein employed contain only two terminal groups which are reactive to formaldehyde, i.e., they are difunctional from the standpoint of methylol-forming reactions. As is well known, although onemay start with difunctional phenols, and depending on the procedure employed, one may obtain cross-linking which indicates that one or more of the phenolic nuclei have been converted from a difunctional radical to a trifunctional radical, or in terms of the resin, the molecule as a whole has a methylol-forming reactivity greater than 2. Such shift can take place after the resin has been formed or during resin formation. Briefly, an example is simply where an alkyl radical, such as methyl, ethyl, propyl, butyl, or the like, shifts from an ortho position to a meta position, or from a para position to a meta position. For instance, in the case of phenol-aldehyde varnish resins, one can prepare at least some in which the resins, instead of having only'two points of reaction can have three, andpossibly more points of reaction, with formaldehyde, or any other reactant which tends to form a methylol or substituted methylol group.

The resins herein employed are soluble in a nonoxygenated hydrocarbon solvent, such as benzene or xylene.

The resins herein employed as raw materials must be comparatively low molal products having on the average 3 to 6 nuclei per resin molecule.

The condensation products here obtained, Whether in the form of the free base or the salt, do not go over to the insoluble stage on heating. The condensation product obtained according to the present invention is heat stable and, in fact, one of its outsanding qualities is that it can be subjected to oxyalkylation, particularly oxyethylation or oxypropylation, under conventional conditions, i.e., presence of an alkaline catalyst, for example, but in any event at a temperature above C. without becoming an insoluble mass.

What has been said previously in regard to heat stability, particularly when employed as a reactant for preparation of derivatives, is still important from the standpoint of manufacture of the condensation products themselves insofar that in the condensation process employed in preparing the compounds described subsequently in detail, there is no objection to the employing of a temperature above the boiling point of water. As a matter of fact, all the examples included subsequently employ temperatures going up to to C.

What is said above deserves further amplification at this point for the reason that it may shorten 'what is said subsequently in regard to the production of the herein described condensation products. Since formaldehyde generally is employed economically in an aqueous phase.

(30% to 40% solution, for example) it is necessary to have manufacturing procedure which will allow reactions to take place at the interface of the two immiscible liquids, to wit, the formaldehyde solution and the resin solution, on the assumption that generally the amine will dissolve in one phase or the other. Although reactions of the kind herein described will begin at least at com paratively low temperatures, for instance, 30 C., 40 C., or 50 0., yet the reaction does not go to completion except by the use of the higher temperatures. The use of higher temperatures means, of course, that the condensation product obtained at the end of the reaction must not be heat-reactive. Of course, one can add an oxygenated solvent such as alcohol, dioxane, various ethers of glycols, or the like, and produce a homogeneous phase. If this latter procedure is employed in preparing the herein described condensations it is purely a matter of convenience, but whether it is or not, ultimately the temperature must still pass within the zone indicated elsewhere, i.e.,

somewhere above the boiling point of water unless some obvious equivalent procedure is used.

Any reference, as in the hereto appended claims, to the procedure employed in the process is not intended to limit the method or order in which the reactants are added, cornmingled or reacted. The procedure has been referred to as a condensation process for obvious reasons. As pointed out elsewhere it is my preference to dissolve the resin in a suitable solvent, add the amine, and then add the formaldehyde as a 37% solution. However, all three reactants can be added in any order. I am inclined to believe that in the presence of a basic catalyst, such as the amine employed, that the formaldehyde produces methylol groups attached to the phenolic nuclei which, in turn, react with the amine. It would be immaterial, of course, if the formaldehyde reacted with the amine so as to introduce a methylol group attached to nitrogen which, in turn, would react with the resin molecule. Also, it would be immaterial if both types of compounds were formed which reacted with each other with the evolution of a mole of formaldehyde available for further reaction. Furthermore, a reaction could take place in which three different molecules are simultaneously involved although, for theoretical reasons, that is less likely. What is said herein in this respect is simply by way of explanation to avoid any limitation in regard to the appended claims.

PART 2 It is well known that one can readily purchase on the open market, or prepare, fusible, organic solvent-soluble,

In the above formula n represents a small whole number varying from 1 to 6, 7 or 8, or more, up to probably 10 or 12 units, particularly when the resin is subjected to heating under a vacuum as described in the literature. A limited sub-genus is in the instance of low molecular weight polymers where the total number of phenol nuclei varies from 3 to 6, i. e., n varies from 1 to 4; R represents an aliphatic hydrocarbon substituent generally an alkyl radical having from 4 to 14 carbon atoms, such as a butyl, amyl, hexyl, decyl or dodecyl radical. Where the divalent bridge radical is shown as being derived from formaldehyde it may, of course, be derived from any other reactive aldehyde having 8 carbon atoms or less.

The resins herein employed as raw materials must be soluble in a nonoxygenatedsolvent, such as benzene or xylene. This presents no problem insofar that all that is required is to make a solubility test on commercially available resins, or else prepare resins which are xylene or benzene-soluble as described in aforementioned U. S. Patent No. 2,499,365, or in U. S. Patent No. 2,499,368, dated March 7, 1950, to De Groote and Keiser.

If one selected a resin of the kind just described previously and reacted approximately one mole of the resin with two moles of formaldehyde and two moles of a basic nonoxyhydroxylated secondary amine as specified, following the same idealized over-simplification previously referred to, the resultant product might be illustrated thus:

R\ OH I-OH H R N--O C- -C CN/ H H H H R R 'n. R

The basic amine may be designated thus:

R! HN/ subject to what has been said previously as to the presence of a substituted imidazoline or a substituted tetrahydropyrimidine radical having at least one basic secondary amine radical present and that the ring compound,

or rather the two occurrences of R jointly with n, be

free from a primary amine radical. However, if one attempts to incorporate into the formula a structure such as a substituted imidazoline or substituted tetrahydropyrimidine such as the following:

N- G H:

C "Has-.0

then one becomes involved in added diificulties in presenting an overall picture. Thus, for sake of simplicity the ring compound having the reactive secondary amino group will be depicted as As has been pointed out previously, as far as the resin unit goes one can use a mole of aldehyde other than formaldehyde, such as acetaldehyde, propionaldehyde or butyraldehyde.

in which R is the divalent radical obtained from the particular aldehyde employed to form the resin. For reasons which are obvious the condensation product obtained appears to be described best in terms of the method of manufacture.

As previously stated the preparation of resins, the kind herein employed as reactants, is well known. See previously mentioned U. S. Patent No. 2,499,368. Resins can be made using an acid catalyst or basic catalyst or a catalyst having neither acid nor basic properties in the ordinary sense or without any catalyst at all. It is preferable that the resins employed be substantially neutral. In other words, if prepared by using a strong acid as a catalyst, such strong acid should be neutralized. Similarly, if a strong base is used as a catalyst it is preferable that the base be neutralized although I have found that sometimes the reaction described proceeded more rapidly in the presence of a small amount of a free base. The amount may be as small as a 200th of a percent and as much as a few l0ths of a percent. Sometimes moderate increase in caustic soda and caustic potash may be used. However, the most desirable procedure in practically every case is to have the resin neutral.

In preparing resins one does not'get a single polymer, i. e., one having just 3 units, or just 4 units, or just 5 units, or just 6 units, etc. It is usually a mixture; for instance, one approximating 4 phenolic nuclei will have some trimer and pentamer present. Thus, the molecular weight may be such that it corresponds to a fractional value for n as, for example, 3.5, 4.5 or 5.2.

The resin unit may be exemplified thus:

In the actual manufacture of the resins I found no reason for using other than those which are lowestin price and most readily available commercially. For purposes of convenience suitable resins are characterized in the following table:

TABLE I M01. wt Ex- R'" of resin ample R Position derived 'n molecule number of B om- (based 0n n+2) Phenyl Para... 3.5 992.5

3.5 805.5 3.5 1,036.5 152-2 35 1134415 yl 3.5 1,498.5 Tertiary butyl 3.5 845.5

Tertiary amyl 3. 5 1, 022. 5 Nonyl 3. 5 1, 330. 5 Tertiary butyl 3.5 1,071.5 Tertiary amyi 3. 5 1, 148. 5 Non 3. 5 1, 456. 5 Tertiary butyi 3. 5 1, 008. 5

Tertiary amyl 3. 5 1, 085.5 Nonyl 3.5 1, 393. 5 Tertiary butyl 4.2 996.6

Tertiary amyl 4. 2 1, 083. 4 Non 4. 2 1, 430. 6 4.8 1,094.4 4.8 1,189.5 4.8 1,570.4 22:8 1.5 1.5 053.0 1.5 688.0

PART 3 The expression cyclic amidines is employed in its usual sense to indicate ring compounds in which there are present either 5 members or 6 members, and having 2 nitrogen atoms separated by a single carbon atom supplemented by either two additional carbon atoms or three additional carbon atoms completing the ring. All the carbon atoms may be substituted. The nitrogen atom of the ring involving two monovalent linkages may be substituted. Needless. to say, these compounds include members in which the substituents also may have one or more nitrogen atoms, either in the form of amino nitrogen atoms or in the form of acylated nitrogen atoms. Reference is made to applications Serial Nos. 288,746 and 296,087 for a discussion of the cyclic amidines which may be used in producing the compounds used in accordance with the present invention.

Examples selected include the following:

%N*GH7 Gillies-C I fC' H 2-undecy1imidazo1ine N-oH, 17 350 I III-CH: H Z-heptadecylimidazoline Z-methyl,1-hexadecylaminoethylaminoethylimidazoline N- 0 Ha C3H0.NH. CigHn l-dodecylaminopropylimidazoline NCH2 11.0

N GH:

CgH4.NH.C2H4O CH.C1'IH35 1- stearoyloxyethyl) aminoethylimidazoliue NCH2 CzH4.NH. CaH4NHO (3.0111135 l-stearamidoethylaminoethylimidazoiine N-O'Ha NCHz O2H .I;I. CzH4.NHO C .CH;

1- u-dodecyl -acetamidoethylaminoethylimidazoliue .Z-heptadecyl,l-methylaminoethyl tetrahydropyrimidine 4-methyl,Z-dodecyl,1-methylaminoethylaminoethyl tetrahydi'opyrimidine As has been pointed out previously, the reactants herein employed may have two substituted imidazoline rings or two substituted tetrahydropyrimidine rings. Such compounds are illustrated by the following formula:

As to compounds having a tertiary amine radical, it is obvious that one can employ derivatives of polyamines in which the terminal groups are unsymmetrically alkylin which R represents a small alkyl radical such as methyl, ethyl, propyl, etc., and n represents a small whole number greater than unity such as 2, 3 or 4.

Ring compounds, such as substituted imidazolines, may be reacted with a substantial amount of alkylene oxide as noted in the preceding paragraph and then a secondary amino group introduced by two steps; first, reaction with an ethylene imine, and second, reaction with another mole of the oxide, or with an alkyl-ating agent such as dimethyl sulfate, benzyl chloride, a low molal ester of a sulfonic acid, an alkyl bromide, etc.

Other suitable means may be employed to eliminate a terminal primary amino radical. If there is additionally a basic secondary amino radical present then the primary amino radical can be subjected to acylation notwithstanding the fact that the surviving amino group has no significant basicity. As a rule acylation takes place at the terminal primary amino group rather than at the secondary amino group, thus one can employ a compound such as NC Hr CnHaa- N-OH:

I C:Hi.NH. CaH4.NHn 2-heptadecyl,l-diethylenediaminoimidazoline and subject it to acylation so as to obtain, for example,

acetylated 2-heptadecyl,1-diethylenediaminoimidazoline of the following structure:

Similarly, a compound having no basic secondary amino radical but a basic primary amino radical can be reacted with a mole of an alkylene oxide, such as ethylene oxide, propylene oxide, glycide, etc., to yield a perfectly satisfactory reactant for the herein described condensation procedure. This can be illustrated in the following manner by a compound such as NGH2 CzH4.NH2 2-heptadecyl,l-aminoethylimidazollne which can be reacted with a single mole of ethylene oxide, for example, to produce the hydroxy ethyl derivative of 2-heptadecyl,l-amino-ethylimidazoline, which can be illustrated by the following formula:

/NCH2 Cn arC N-CH:

CrHrOH C2H4. C (17) N-CHz CaHr. C

N-CH3 l,

N-on,

III-C H2 H PART 4 The products obtained by the herein described processes represent cogeneric mixtures which are the result of a condensation reaction or reactions. Since the resin molecule cannot be defined satisfactorily by formula, although it may be so illustrated in an idealized simplification, it is difficult to actually depict the final product of the cogeneric mixture except in terms of the process itself. The condensation of the resin, the cyclic amidine and formaldehyde is described in detail in applications Serial Nos. 288,746 and 296,087 and reference is made to those applications for a discussion of the factors involved.

Little more need be said as to the actual procedure employed for the preparation of the herein described con- 11 densation products. The following example will serve by way of illustration:

Example 1b :12 to approximately 3 to '6 hours. Note that in Table II following there are a large number of added examples illiis'trating the same procedure. In each case the initial mixture was stirred and held 'a't'a fairly low temperature The phenol-aldehyde resin is the one that has been (30 to 40 C.) for-a period of several hours. Then reidentified previously as Example 2a. It was obtained from a para-tertiary butylphenol and formaldehyde. The resin was prepared using an acid catalyst which was completely neutralized at'the end of the reaction. The molecular weight of the resin was 882.5. This corresponded to an average of about 3% phenolic nuclei, as the value for n which excludes the 2 external nuclei, i. e., the resin was largely a mixture having 3 nuclei and 4 nuclei excluding the 2 external nuclei, or 5 and 6 overall nuclei. The resin so obtained in a neutral state had a light amber color.

882 grams of the resin identified as 2a, preceding, were fluxing was employed until the odor of formaldehyde disappeared. After the odor of formaldehyde disappeared the pha's'e sep'a'ratingtrap was employed 'to separate out all the water, both the solution and condensation. After 10 all the water had been separated enough xylene was taken out to have the final product reflux for several hours somewhere in the range of 145 to 150 C., or thereabouts. Usually the mixture yielded a clear solution by the time the "bulk of the water, or all of the water, had

been removed.

Note that as pointed out previously, this procedure is illustrated by 24 examples in Table II.

TABLE II Strength of Reac- Reae- Mar. Ex Resin Amt Amine used Amt. of formaldehyde Solvent used tion tion distill. No used grs. amine, soln. andamt; and amt. temp., time temp.

grams C. (hrs) C 612 37%, 162 g." Xylene, 600 g -25 148 306 37%, 81.g- Xylene, 450 21-23 24 145 306 do Xylene, 600 gm. 20-22 28 150 281 30%, 100 g Xylene, 400 g. 22-24 28 148 281' do Xylene, 450 g... 21-23 30 141i 37%, 81 g "Xylene, 600g 21-25 26 146 d Xylene, 400 g-. 23-28 .20 147 Xylene, 450 "m. 22-26 26 146 Xylene, 600 gm. 21-25 38 150 Xylene, 450 g 20-24 36 149 Xylene, 500 g. 21-22 24 142 Xylene, 650 g 20-21 26 145 Xylene, 4259... 22-28 28 146 Xylene, 450 g 23-30 27 150 Xylene, 550 g 20-24 29 147 Xylene, 440 g 20-21 30 148 Xylene, 480 g 21-26 32 146 Xylene, 600 g 21-23 26 147 Xylene, 500 g 21-82 29 150 .do 21-30 32 150 Xylene, 550 21-23 37 150 126 do Xylene, 440 g 20-22 30 150 126 do v Xylene, 600 g 20-25 36 140 126 30%, g Xylene, 400 g 20-24 32. 152

powdered and mixed with a somewhat lesser amount or xylene, i. e., 600 grams The mixture was refluxed until 45 case the formaldehyde used was a 37% solution and 162 7 grams were added in approximately 3 hours. The mixture was stirred vigorously and kept within a range of approximately 40 to 44 C., for about 16 hours. At the end of this time it was refluxed, using a phase-separating trap and a small amount of aqueous distillate withdrawn from time to time. The presence of unreacted formaldehyde was noted. Any unreacted formaldehyde seemed to disappear in approximately three hours after refluxing started. As soon as the odor of formaldehyde was no longer detectible the phase-separating trap was set as to eliminate all the water of solution and reaction. After the water was eliminated part of the xylene was removed until the temperature reached approximately 148 C. The mass was kept at this higher temperature for 3 or 4 hours. During this time any additional water, which was probably water of reaction which had formed, was eliminated by means of the trap. The residual xylene was permitted to stay in the cogeneric mixture. A small amount of the sample was heated on a water bath to remove the excess xylene. The residual material was dark red in color and had the consistency of a thick sticky fluid or tacky resin. The overall reaction time was approximately 30 hours. In other examples, it varied from as little as 24 hours up to approximately 38 hours. The time can be reduced by cutting the low temperature period The amine numbers referred to are the ring compounds identified previously by number in Part 3.

PART 4 In preparing oxyalkylated derivatives of products of "the kind which appear as examples in Part 3, I have found it particularly advantageous to use laboratory equipment which permits continuous oxypropylation and oxye thylation. More specific reference will be made to treatment with glycide subsequently in the text. The oxyethylation step is, of course, the same as the oxypropylation step insofar that two low boiling liquids are handled in each instance. What immediately follows refers to oxyethylation and it is understood that oxypropylation can be handled conveniently in exactly the same manner. The oxyalkylation of the amine resin condensates is carried out by procedures which are commonly used for the oxyalkylation of oxyalkylation susceptible materials. The factors to be considered are discussed in some detail in applications Serial Nos. 301,807 and 310,555 and reference is made to those applications for a description of suitable equipment, precautions to be taken and a general discussion of operating technique. The following examples are given by way of illustration.

Example 10 The oxyalkylation-susceptible compound employed is the one previously described and designated as Example dehyde. 15.18 pounds of this resin condensate were disvarious oil field emulsions.

13 solved in 6 pounds of solvent (xylene) along with 1.0 pound of finely powdered caustic soda as a catalyst. Adjustment was made in the autoclave to operate at a temperature of approximately 125 C. to 135 C., and at a pressure of about 20 to 25 pounds. In some subsequent examples pressures up to 35 pounds were employed.

The time regulator was set so as to inject the ethylene oxide in approximately three-quarters of an hour and then continue stirring for 15 minutes or longer, a total time of one hour. The reaction went readily, and, as a matter of fact, the oxide was taken up almost immediately. The speed of reaction, particularly at the low pressure, undoubtedly was due in a large measure to excellent agitation and also to the comparatively high concentration of catalyst. The amount of ethylene oxide introduced was equal in weight to the initial condensation product, to wit, 15.18 pounds. This represented a molal ratio of 34.5 moles of ethylene oxide per mole of condensate.

The theoretical molecular weight at the end of the reaction period was 3036. A comparatively small sample, less than 50 grams, was withdrawn merely for examination as far as solubility or emulsifying power was concerned and also for the purpose of making some tests on The amount withdrawn was so small that no cognizance of this fact is included in the data, or subsequent data, or in the data presented in tabular form in subsequent Tables 3 and 4.

The size of the autoclave employed was 25 gallons. In innumerable comparable oxyalkylations I have withdrawn a substantial portion at the end or" each step and continued oxyalkylation on a partial residual sample. This was not the case in this particular series. Certain examples were duplicated as hereinafter noted and subjected to oxyalkylation with a difierent oxide.

Example 20 This example simply illustrates the further oxyalkylation of Example 10, preceding. As previously stated the oxyalkylation-susceptible compound, to wit, Example 1b, present at the beginning of the stage was obviously the same as at the end of the prior stage (Example Is), to wit, 15.18 pounds. The amount of oxide present in the initial step was 15.18 pounds, the amount of catalyst remained the same, to wit, 1.0 pound, and the amount of solvent remained the same. The amount of oxide added was another 15.18 pounds, all addition of oxide in these various stages'being based on the addition of this particular amount. Thus, at the end of the oxyethylation step the amount of oxide added was a total of 30.36 pounds and the molal ratio of ethylene oxide to resin condensate was 69.0 to 1.0. The theoretical molecular weight was 3348.

The maximum temperature during the operation was 125 C. to 130 C. The maximum pressure was in the range of 20 to 25 pounds. The time period was one and one-half hours.

Example 30 The oxyalkylation proceeded in the same manner described in Examples 1c and 20. There was no added solvent and noadded catalyst. The oxide added was 15.18 pounds and the total oxide at the end of the oxyethylation step was 45.54 pounds. The molal ratio of oxide to condensate was 103.5 to 1. Conditions as far as temperature and pressure and time were concerned were all the same as in Example and 2c. The time period was somewhat longer than in previous examples, to wit, 3 hours.

Example 40 The oxyethylation was continued and the amount of oxide added again was 15.18 pounds. There was no added catalyst and no added solvent. The theoretical molecular weight at the end of the reaction period was 6072. The molal ratio of oxide to condensate was 138.0 to 1. Conditions as far as temperature and pressure were concerned were the same as in previous examples. The time period was slightly longer, to wit, 3 hours. The reaction unquestionably began to slow up somewhat.

Example 50 The oxyethylation continued with the introduction of another 15.18 pounds of ethylene oxide. No more solvent was introduced but .3 pound causticsoda was added. The theoretical molecular weight at the end of the agitation period was 9108, and the molal ratio of oxide to resin condensate was 172.5 to 1. The time period, however, dropped to 3 hours. Operating temperature and pressure remained the same as in the previous example.

Example 60 The same procedure was followed as in the previous examples. The amount of oxide added was another 15.18 pounds, bringing the total oxide introduced to 91.08 pounds. The temperature and pressure during this period were the same as before. There was no added solvent. The time period was 3% hours. Molal ratio of oxide to resin condensate was 207.0 to one.

Example 70 The same procedure was followed as in the previous six examples without the addition of more caustic or more solvent. The total amount of oxide introduced at the end of the period was 106.26 pounds. The theoretical molecular weight at the end of the oxyalkylation period was 12,144. The time required for the oxyethylation was a bit longer than in the previous step, to wit, 4 hours.

Example 8c This was the final oxyethylation in this particular series. There was no added solvent and no added catalyst. The total amount of oxide added at the end of this step was 121.44 pounds. The theoretical molecular weight was 13,662. The molal ratio of oxide to resin condensate was 276.0 to one. Conditions as far as temperature and pressure were concerned were the same as in the previous examples and the time required for oxyethylation was 4 hours.

The same procedure as described in the previous examples was employed in connection with a number of the other condensates described previously. All these data have been presented in tabular form in a series of four tables, Tables III and IV, V and VI.

In substantially every case a 25-gallon autoclave was employed, although in some instances the initial oxyethylation was started in a l5-gallon autoclave and then transferred to a 25-gallon autoclave. This is immaterial but happened to be a matter of convenience only. The solvent used in all cases was xylene. The catalyst used was finely powdered caustic soda.

Referring now to Tables III and IV, it will be noted that compounds 1c through 40c were obtained by the use of ethylene oxide, whereas 410 through 800 were obtained by the use of propylene oxide alone.

Thus, in reference to Table III it is to be noted as follows:

The example number of each compound is indicated in the first column.

The identity of the oxyalkylation-susceptible coma pound, to wit, the resin, condensate, is indicated in the second column.

The amount of condensate is shown in the third column.

Assuming that ethylene oxide alone is employed, as happens to be the case in Examples 10 through 400, the amount of oxide present in the oxyalkylation derivative is shown in column 4, although in the initial step since no oxide is present there is a blank.

When ethylene oxide is used exclusively the 5th column is blank.

Moloc. wt. based on theoretical value Since comoxide to oxy- Molal ratio oxide to oxyaikyl. aikyl. suscept. suseept.

Ethyl. Propi.

cmpd. crnpd.

Solvent, lbs.

signated by d numbers, 1d, 2d,

in the c series, for example 36c,

Then oxyalkylation proceeded by Composition at end lbs.

555533335555555500000000000055550000333} LLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLlllllllll These compounds involve the use of Prop]. Cataoxide, lys

lbs.

'nvolve the use of ethylene oxide first, and propyl- Ethi. oxide, lbs.

e. It'sometimes happens that although xylene in com- Referring to Table IV, Examples 400 through 800 are Therefore, as explained previously, four columns Reference is now made to Table V. It is to be noted In the preparation of this series indicated by the small In examining the table beginning with 1d, it will be o-s* cmpd., lbs.

sallzlzillttttttiiaaaaaaaa mwlllmmwmmmwmml1111111111111111111111111 present, with several volumes of water, xylene and kerosen paratively small amounts will dissolve in the concentrated material, when the concentrated material in turn is diluted 5 with xylene separation takes place.

the counterpartsof Examples lc through 40c, except that the oxide employed is propylene oxide instead of ethylene oxide.

these compounds are de 3a, etc., through and including 32d. They are derived, in turn, from compounds both ethylene oxide and propylene oxide. pounds 1c through 400 were obtained by the use of ethylene oxide, it is obvious that those obtained from 360 and 400,

tained from 54c and 76c obviously come from a prior series in which propylene oxide was used first.

letter d, as 1d, 2d, 3d, etc., the initial 0 series such 25 as 360, 40c, 54c, and 760, were duplicated and the oxyalkylation stopped at the point designated instead of being carried further as may have been the case in the original oxyalkylation step. using the second oxide as indicated by the previous explanation, to wit, propylene oxide in 1d through 16d, and ethylene oxide in 17d through 32d, inclusive.

noted that the initial product, i. e., 36c, consisted of the TABLE III Solvent, lbs.

5555333355553333000055.050000555500003333 LLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLll Prool. Cataoxide, lyst,

Composition before Ethl. oxide, lbs;

lation step and the third lbs.

and the 7th column shows the empd, cmpd., ex. No.

the oxylalky The =6th column shows the amount of powdered caustic soda used as a catalyst amount of solvent employed.

The 8th column can be ignored where a single oxide was employed.

The 9th column shows the theoretical molecular 'weigh't 'at the end of the oxyalkylation period.

The 10th column states the amount of condensate present in the reaction mass at the end of the period.

As pointed out previously, in this particular series the 10 bii1n",t0 Columns 11 and amount of reaction mass withdrawn for examination was so small that it was ignored and for this reason the resin condensate in column 10 coincides with the figure in column 3.

Column 11 shows the amount of ethylene oxide em- 15 40c, 54c, and 76c. .ployed in the reaction mass at the end of the particular period.

Column 12 can be ignored insofar that no propylene oxide was employed.

Column 13 shows the catalyst at the end of the reacene oxide afterward. Inversely, those compounds obtiojn period.

Column 14 shows the amount of solvent at the end of the reaction period.

Column 15 shows the molal ratio of ethylene oxi e to condensate.

Column 16 can be ignored for the reason that no propylene oxide was employed.

Referring now to Table VI. It is to be noted that the first column refers to Examples 1c, 20, 30, etc.

The second column gives the maximum temperature employed during column gives the maximum pressure.

The fourth column gives the time period employed. The last three columns show solubility tests by shakin i a small amount of the compound, including the solvent reaction product involving 15.18 pounds of the resin con- Ex. No.

ic 1b-..

'Oxyaikylation-susceptible.

17 densate, 22.27 pounds of ethylene oxide, 1.0 pound of caustic soda, and-6.0 pounds of -thesol-vent.--

It is to be noted that reference to.-.the .eatalysmn Table V refers to the tot-al-amount-of catalyst, i. e.,- the-catalyst present from the first oxyalkylatiomstep plus added catalyst, if any. Theysame-is truein-regard to the .solvent.

Reference to the solvent .refer sto' the total solvent :present, i. e., that from -'the first: oxyalkyl ation.;step -plus added solvent, if any.

In this series, it will be noted that the theoretical molecular weights are given prior to the oxyalkylation step and after the oxyalkylationzstep, although the value at. the end of onesstep is :thevalue at the beginning'ofnthew next step, except. obviously. at the. very start ;the value-:de pends on the theo'reticalmolecular weight at the end of the initial oxyalkylationstep; i..e., oxyethylation for 1d through 16a, and 'oxypro'pylationtor- 17d through 32d.

It will be noted. also that under the molal ratiothe. values of both -:oxides gto.the-resin;condensate are eineluded.

The data given -in regard tosthe operating 00115113191157; is substantially the. same as before and appears in .Table .1

The products. resulting-fromthese procedures maycon:

particularly vacuum distillation.

thus obtain whatmay betermedanindiflerent.oxya1kyla=.

tion, i. e., no attempt to selectively add one and then 35 the other, or any other variant.

Needless to say, one could start with ethylene oxide and then use propyleneoxide, and thengo back to ethylene oxide; or, inversely, start with propylene oxide, then use ethyleneoxide, and .then .go .back .to propylene .oxide; or, one could use va combination in which butylenecxide is used along with either one .of the two oxides justmentioned, or.a combination of both :of them.

The colors of the :products usually vary from a reddish amber tint to a definitely red, and amber. The reason is primarily that no;effort :is made to obtain colorless resins initially and the resins themselves may be yellow, amber, or even dark amber. Condensation of a nitrogeneous produjctinvariably yields a darker product than the, original resin andusually {has a reddish color. The solvent employed, if xylene, .addsi nothing to the color but one may use a darker colored aromaticpetroleum solvent. Oxyalkylation generally tends to yield lighter colored prodnets .and {the more oxide employed the lighter the color of the product; Products can be prepared in-.which the final color is arlighter ,amberwith a reddish tint. Such products can bedecolorized by the useof clays, bleaching chars, etc. Asv far as-use. in=demulsificatiojn isconcerned, or-some other industrialuses, there is no justification for the cost; of bleaching the product.

Generally speaking, the amount .ofalkaline catalyst Presentis comparatively small'and it need not be removed. Since the. products per se are alkaline dueto the presence of ,a basic nitrogen, the removal of the alkaline catalyst is somewhat more difficult than;ordinarily in the case for the reason that if one adds hydrochloric acid, .for example,.to neutralizethe alkalinity one may partially neutralize thebasic nitrogen radica-l. also. The-preferred'proceriure is; to ignore the presence of theflalkaliunless it is objectionable ..or. e1se...add .av stoichiometric ..amo.unt of concentrated hydrochloric acid .equal -.to. the caustic soda present.

TABLE IV Composition before-' Composition at end Molal-ratio v v Molec. Ex. No. 1 'T wt.

-8 0-8 Ethl. Propl. Catn- 801- O-S' Ethl. Propl. Cata- Sol- Ethyl. Propl. based empd., cmpd., oxide, oxide, lyst, vent, cmpd., oxld oxide, lyst, vent, oxide oxide on theex. N 0. lbs. lbs. lbs. lbs. lbs. lbs. lbs. lbs. lbs. lbs. to oxyto, oxyoretical alkyl. alkyl. value suscept. suscept. cmpd. empd.

15,13 1. 1 6.0 15.18 '15.18 1. 1 6.0 26. 2 3, 036 15. 18 15. 18 1. 1 6.0 15.18 30. 36 1. 1 v 6.0 52. 4 4, 554 15. 18 30. 36 1. 1 6.0 15. 18 45. 54 1. 1 6. 0 78. 6 6, 072 15. 18 45. 54 1. 1 6.0 15, 18 60. 72 1. 1 i 6.0 104. 8 7, 590 15.18 60. 72 l. 1 6.0 15. 18 75.90 1. 1 6.0 181. 0 10, 626 15. 18 75. 90 1. 6. 0 15. 18 106. 26 1. 5 6.0 183.4 13, 662 15. 18 106. 26 1. 5 6.0 15. 18 136. 62 1. 5 6. 0 235. 8 16, 698 15. 18 136. 62 1. 5 6.0 15. -18 166. 98 l. 5 6.0 288. 2 18,216 15.46 1.1 4.5 15.46 15.46 1.1 4. 5 26. 6 3, 902 15.46 15.46 1.1 4. 5 15. 46- -30. 92 1.1 4; 5 53. 2 4, 638 15.46 30. 92 1.1 4. 5 15. 46 46; 38 1.1 4. 5 .79. 8 6,184 46 46.38 1.1 4. 6 15.46 61.84 1.1 4. 5 106.4 7, 730, 15.46 61. 84 1. 1 4. 5 15. 46 77. 1. 1 4. 5 133.0 10,822 15.46 77. 30 1. 5 4. 5 15.46 108. 22 1. 5 4. 5 186. 2 l 914 15.46 108.22 1. 5 4. 5 15. 46- 139. 14 1. 5 4. 5 .238. 4 17, 006 15.46 139. 14 1. 5 4. 5 15.46 170.06 1. 5 4. 5 292. 6 e 552 17. 74 1. 2 4. 5 17. 74 '17. 74 1. 2 4. 5 30. 6 3, 548 17. 74 17.74 1. 2 4. 5 17. 74 35. 48 1. 2 4. 5 61.2 5, 322 17. 74 85. 48 1. 2 4. 5 17. 74 53. 22 1. 2 4. 5 91. 8 7, 096 17. 74 53. 22 1. 2 4. 5 17. 74 70. 96 1. 2 4. 5 122. 4 8,870 17. 74 70. 96 1. 2 4. 5 17; 74 88. 1. 2 4. 5 153.0 12,418 17. 74 88. 70 1. 7 4. 5 17:74 124. 18- 1. 7 4. 5 214. 2 15, 966 17. 74 124.18 1.7 4. 5 17. 74 1'59. 66 1. 7 4. 5 275. 4 19, 514 17. 74 159. 66 1. 7 4. 5 17. 74 195. 14 1. 7 4. 5 336. 6 21, 288 11.58 1. 0 4. 4 11; 58- 'll; 58 1. 0 4. 4 19. 95 2, '316 11. 58 11.58 1. 0 4:4 11.58 23,16 1. 0 4. 4 39. 90' 3, 474 11.58 23.16 1.0 4. 4 11; 58 34. 74 1. 0 4. 4 .59. 4, 632 11.58 34. 74 1. 0 4. 4 11.58 46. 32 1. 0 4. 4 79. 80 5, 790 11.58 46. 32 1. 0 4. 4 11.58 57. 1. 0 4. 4 '99. 60 8,106 .11. 58 57. 90 1. 5 4. 4 11. 58- 81.06 1. 5 4. 4 140. 0 10, 422 11. 78 81.06 I 1. 5 4.4 ,11'. 58 104; 22 1. 5 4.4 180.0 12, 738 11. 58 104. 22 1. 5 4. 4 ll: 58' 127: 38 1. 5 4. 4 219. 9 13, 896 15. 18 1. 0 6:0 "15: '18 7. 59 1. 0 6.0 13. 15 2, 279 15. 18 7. 59'" 1 ,0, 6. 0 :15. '18 15. 18 1. 0 6.0 26. 3 3, 036 15.18 15.18 1. 0 6:0 15; 18 22; 77- 1. 0 6.0 39. 45 3,795 15. 18 22. 77 1.0 6.0 -15. 18 30. 36 1.0 6- 0,. .52. 60 4, 553 15. 18 30. 36 1. 0 60 j 15. '18 37; 1. 0 6. 0, 65. 75 5, 313 15. 18 37. 95 1. 4 6.0 "15. 18' 53. 13' 1. 4 6.0 92. 05' 6, 831 15.18 53.13 z I 1. 4 6.0 15.18 68. 31 1. 4 6. 0 1'18. 35 8, 349 15. 18 68. 31' 1. 4 e 6.0 15. -18 83. 49 1. 4 6. 0. 144. 65" 867 Oxyalkylation-susceptible.

TABLE V Composition before Composition at end Molalratlo Melee.- Ex. No. 'wt. O-S O-S Ethl. Propl. Gata- S01- 0-S Ethl. Pro 1. Oata- Sol- Ethyl. Propl. based cmpd., cmpd., oxide, oxide, lyst, vent, cmpd., oxide, 0x1 9, lyst, vent, oxide oxlde on theex.No. lbs. lbs. lbs. lbs. lbs. lbs lbs. s. lbs. lbs. to oxyto oxyoreticalalkyl. alkyl. valuesuscept. suscept. cmpd. cmpd.

360-... 15.18 30.36 1.0 6.0 15.18 30.36 7.59 1.0 6.0 68.8 13.10 5,313' 36c.. 15.18 30.36 59 1.0 6.0 15.18 30.36 15.18 1.0 6.0 68.8 26.15 6,072 3611.--. 15.18 30.36 15.18 1.0 6.0 15.18 30.36 22.77 1.0 6.0 68.8 39.20 6,831 360.... 15.18 30.36 22.77 1.0 6.0 15.18 30.36 30.36 1.0 6.0 68.8 52.3 7,590 360..-. 15.18 30.36 30.36 1.0 6.0 15.18 30.36 37.95 1.0 6.0 68.8 60.5 8,349 360.... 15.18 30.36 37.95 1.0 6.0- 15.18 30.36 45.54 1.5 6.0 68.8 78.6 9,108 360..-. 15.18 30.36 45.54 1.5 6.0 15.18 30.36 60.72 1.5 6.0 68.8. 104.8 10,626 360.--. 15.18 30.36 60.72 1.5 6.0 15.18 30.36 75.90 1.5 6.0 68.8 131.8 12,144 400.--. 15.18 60.72 1.3 6.0 15.18 60.72 7.59 1.3 6.0 137.6 13.1 8,349 400.... 15.18 60.72 7.59 1.3 6.0 15.18 60.72 15.18 1.3 6.0 137.6 26.2 9,108 4%.... 15.18 60.72 15.18 1.3 6.0 15.18 60.72 30.36 1.3 6.0.1316 52.4 10,626 400.--. 15.18 60.72 30.36 1.3 6.0 15.18 60.72 45.54 1.3 6.0 137.6 78.6 12,144 400.... 15.18 60. 72 45.54 1.3 6.0 15.18 60.72 60.72 1.8 6.0 137.6 104.8 13,662- 400.... 15.18 60. 72 60.72 1.8 6.0 15.18 60.72 68.21 1.8 6.0 137.6 117.9 14,421 400.--- 15.18 60.72 68.21 1.8 6.0 15.18 60.72 75.90 1.8 6.0 137.6 131.0 15,180 400.--. 15.18 60.72 75.90 1.8 6.0 15.18 60.72 91.08 1.8 6.0 137.6 157.2 16,698 540-.-. 15.46 108.22 1.5 4.5 15.46 3.86 108.22 1.5 4.5 8.75 186.2 ,300 540.--. 15.46 3.86 108.22 1.5 4.5 15.46 7.73 108.22 1.5 4.5 17.6 186.2 14,687 54c..-. 15.46 7.73 108.22 1.5 4.5 15.46 15.46 108.22 1.5 4.5 35.2 186.2 15,460 540.... 15.46 15.46 108.22 1.5 4.5 15.46 23.19 108.22 1.5 4.5 52.8 186.2 ,333 5417.-.- 15.46 23.19 108.22 1.5 4.5 15.46 30.92 108.22 1.5 4.5 70.3 186.2 17,100 45c 15.46 30.92 108.22 1.5 4.5 15.46 38.65 108.22 1.5 4.5 87.9 186.2 17,879 546-... 15.46 38.63 108.22 1.5 4.5 15.46 46.38 108.22 1.5 4.5 105.2 186.2 18,652 540.--. 15.46 46.38 108.22 1.5 4.5 15.46 54.11 108.22 1.5 4.5 123.0 186.2 19,425 760.... 15.18 30.36 1.0 6.0 15.18 7.59 30.36 1.0 6.0 17.25 52.6 5,313 760---- 15.18 7.59 30.36 1.0 6.0 15.18 15.18 30.36 1.0 6.0 34.50 52.6 6,072 760..-. 15.18 15.18 30.36 1.0 6.0 15.18 22.77 30.36 1.0 6.0 51.75 52.6 6,831 76c-. 15.18 22.77 30.36 1.0 6.0 15.18 30.36 30.36 1.0 6.0 69.0 52.6 7.590 766---- 15.18 30.36 30.36 1.0 6.0 15.18 45.54 30.36 1.5 6.0 103.0 53.6 9,108 760.--- 15.18 45.54 30.36 1.5 6.0 15.18 60.72 30.36 1.5 6.0 138.2 52.6 10,626 760-.-- 15.18 60.72 30.36 1.5 6.0 15.18 75.90 30.36 1.5 6.0 172.2 52.0 12,144 760-.-. 15.18 75.90 30.36 1.5 6.0 15.18 91.08 30.86 1.5 6.0 207.0 52.6 13,662

*Oxyalkylation-susoeptible.

TABLE VI Max. Max. Solubility Ex. temo, pres., Time, No. 0. p. 5.1. hrs.

Water Xylene Kerosene 20-25 1 Insoluble 20-25 Emulsifiable. 20-25 Sol blo 20-25 20-25 20-25 20-25 20-25 15-20 15-20 15-20 15-20 15-20 15-20 15-20 15-20 10-15 10-15 10-15 10-15 10-15 10-15 10-15 10-15 30-35 30-35 30-35 30-35 30-35 30-35 30-35 30-35 30-35 30-35 30-35 30-35 30-35 30-35 30-35 30-35 25-35 Insoluble. 25-35 D0. 25-35 Disperslble. 25-35 Solublo. 25-35 Do. 25-35 D0. 25-35 Do. 25-35 D0. 30-35 Insoluble. ao-as Do. so-as Dlsperslble.

Max. Max Solubility Ex. tern pres Time, Not: pas. hrs.

Water Xylene Kerosene 30-35 4% insoluble I l l Disperslbla: 30-35 d Do. 30-35 1 D0. 30-35 Insoluble. 30-35 Do. 30-35 D0. 30-35 Soluble. 30-35 Do. 30-35 Do; 30-35 4 .139. 30-35 4 1 Do. 30-35 5 Do. 30-35 5% .Do. 30-40 1% Insoluble. 30-40 2 i Do. 30-40- 3 Dispersible 30-40 3% uble. 30-40 5 L Do. 30-40- 4 D0. 30-40 4 130. 30-40 6 7 Do -20 2 Insoluble 15-20 2 D0. 15-20 3 Do.- 15-20 4% 1m. 15-20 6 Dlspersible 15-20 5% uble 15-20 D0. 15-20 D0. -35 Insoluble 30-35 D0. 30-35 Do; 30-35 Do, 30-35 Dispersible. 30-35 Soluble; 30-35 Do. 30-35 D0. 30-35 Insoluble 30-35 .13 30-35 Do;- 30-35 D0. 30-35 D0.= 30-35 Do. 30-35 Dispersible; 30-35 Soluble; 30-35 D0. 30-35 D0. 3035 .Do. 30-35 Do; 30-35 D0.- 30-35 A Do; 30-35 Insoluble. 30-35 .D0.'- 15-20 D0. 15-20 ZDo. 15-20 D0. 15-20 Do, 15-20 D0. 15-20 D0. 15-20 Do. 15-20 Do;

PART 6 above the boiling point of water and perhaps at a tem- The conversion of the oxyalkylated basic condensate of the kind 'pr'eviouslydescribed intothe corresponding salt="ofgluc0nic 'acid is a simple operation since it is nothing more .norless than neutralization. Thecondensateinvariably contains H two basic .1 nitrogen .5 atoms. One can neutralize either one or both nitrogen atoms.

Another factor'which requires some consideration would be the presence of basic catalysts which were used during the oxyalkylationprocess. Actual tests indicate that the basicity appears to be somewhat less than would be expected, particularly in examples in which oxyalkylation is comparatively high; The usual procedure has been to add enough gluconic-acid to convert the product into the salt as predetermined and then note whether or not the product showed any marked alkalinity. If-so, slightly more gluconic acid was added until the product was either just barely acid or just very moderately-alkaline. For sake'of clarity this added amount of gluconic acid, it required, is ignored in subsequent Table VIII.-

Gluconic acid is available as a solution. Dehydration causes decomposition; This is not true of the salts,

or at least, the salts of the hereindescribed'oxyalkylated" condensates. Such salts appear to be stable, or stable for all practical purposes, at least at a temperature slightly perature as high as 150 C. or thereabouts.

As has beenpointed out previously ,the present application is a continuation-in-part of certain co-pending applications and reference is made to aforementioned co-pending application, Serial-No.1 329,486, filed January 2, 1953; The co-pending applicationpserial No. 329,486, filed January ,2,.1953, describedthe neutralization of the non-oxyalkylatedcondensate.

Reference is now made to Table VII which, in essence, is substantially the same as much of the data in Table II but includes'additionalcalculationsshowing the amount of gluconi'c'acid (50% )aequiredIto-neutralize a certain amountof condensate';for instance, compare Example la in Table VII, with'Exa'rnple lbrin-Table II. In any event, since there Were-available various oxyalkylated derivatives of condensate 1b and 5b," these particular oxyalkylated derivatives ;;were used for. the purpose of illustrating salt formation, all of "which is illustrated in Table VIIL' Briefly stated, referringtoExample' 1e in Table VII it is to benoted that 1518 grams of-the -nonoxyalkylated condensate required1-480- grams-0f---50% gluconic acid 1518 grams of the condensatet Example 1b, when converted into the oxyalkylated derivative as obtained from 20, were equivalent to 5180 grams. Therefore, 5180 grams were selected as the appropriate amount of oxyalkylated material for neutralization simply for the reason ally the color of the salt is practically the same as the oxyalkylated derivative. For various commercial purposes in which the product is used there is no justification for the added cost of decolorization. The salt form that calculation was eliminated. V can be' dehydrated or rendered solvent-free by the usual The oxyalkylated condensate generally is a liquid and, procedure, i. e., vacuum distillation, after the use of a as a rule, contains a comparatively small amount of solphase-separating trap. vent. Note the examples in Table VIII. The solvent The product as prepared, without attempting to dehappened to be xylene in this instance but could have colorize, eliminates any residual catalyst in the form of 'been benzene, aromatic petroleum solvent, or the like. 10 a salt, and without and particular efiort to obtain abso- Needless to say, the solvent could have been removed lute neutrality or the equivalent, is more satisfactory for from the oxyalkylated derivative by use of vacuum disa number of purposes where the material is useful, such tillation and this is particularly true if benzene happened as a demulsifier for petroleum emulsions of the waterto be the solvent. The product obtained from oxyalkylain-oil type, or oil-in-water type; for the prevention of tion invariably is lighter than the initial material for the rr n of m talli s r especially ferrous reason that the condensate is dark colored and oxyalkylafaces; or as an asphalt additive for anti-stripping purposes. tion simply dilutes the color. In other words, the prod- The condensates prior to oxyalkylation may be solids uct may be almost white, pale straw color, or an amber but are generally viscous liquids or liquids which are shade with a reddish tint. almost solid or tacky. Oxyalkylation reduces such The product either before or after neutralization can materials to viscous liq of thin liquids Comparable be bleached with filtering clays, charcoals, etc. The to p ya y l of course p ing prim rily n he procedure generally is, as a matter of convenience, to amount of alkylene oxide added. After neutralization form the salt and then dilute with a solvent if de ired, the physical characteristics of the products are about the using such solvent as xylene or a mixture of two-thirds Same n in the majority of Cases are q Needless xylene and one-third ethyl al ohol or isopropyl al ohol, to say, if a solvent were added, even if the material were to give approximately a 50% solution. If there happened solid initially, it would be converted into a liquid form. to be any precipitate the solution is filtered. If desired, In light of What has been Said and the Simplicity of the product prior to dilution could be rendered anhydrous salt formation it does not appear that any illustration is simply by adding benzene and subjecting the mixture to required. However, previous reference has been made reflux action under a condensate or a phase-separating to Table VIII. The first example in Table VIII is Extrap. If there happened to be any tendency for the prodample if. The following is more specific data in regard net to separate then the solvents having hydrotropic to Example If. properties, such as the diethylether of ethylene-glycol, Example If or the like, are used.

The salt formatio i merely a tt f agitation at The salt was made from oxyalkylated derivative 2c. room temperature, or at a somewhat higher temperature Oxyalkylated'derivative 2c was made from condensate lb; is desired, particularly in a reflux condenser. Usually Condensate 1b Was made from Resin Example 211 and agitation is continued for an hour but actually neutraliza- Amine 3 which Was z-oleylimidalhline, all Of hich ha tion may be a matter of minutes. In some instances after been Previously desel'ihed- The manufacture of the C011- salt formation is complete and the product is diluted to 40 dehsate required 512 grams of the amine and 162 grams approximately I have permitted the solution to of formaldehyde The Weight of the Condensate on a stand for about 6 to 72 hour So ti de di solvent-free basis was 1518 grams. This represented apon composition, there is a separation of an aqueous'phase proximately 53 grams of basic nitrogen suhleet to What or a small amount of salt-like material. On a laborais Said ehortly hereaftertory scale the procedure is conducted in a separatory Referring to Table VIII it will be noted that 15.18 funnel. If there is separation of an aqueous phase, or pounds of the condensate were combined with 30.36 any other undesirable material, at the bottom of the 'pounds of ethylene oxide and 6 pounds of solvent. In separatory funnel it is merely discarded. The salt form, any event, 4135 grams of the oxyalkylated derivative 2c of course, can be bleached in the same manner as prewere placed in a laboratory device which, although made v1ously described for the oxyalkylated derivative. Usu- 50 of metal, was the equivalent of a separatory funnel. To

TABLE VII Salt formation calculated on Condensateinturn derived frombasis of non-oxyalkylated Salt condensate from Salt conex. den- 37% Wt. of No. sate Amt. Amt. Amine iormconden- Theo. 50% glu No. Resin resin, Solvent sol- Amine used used, aldesate on basic conic N0. gms. vent, gms. hyde, solventnitrogen, acid, gms. gins. freebasis, gms. gms.

gms.

882 Xylene 612 162 1,518 53 1,480 306 81 79a 27 720 30s 81 051 27 720 281 734 as 1,065 281 100 773 as 1,065 281 81 826 as 1,005 394 31 847 42 1,175 394 81 886 42 1,175 3114 81 1, 039 42 1, 395 100 880 42 1,175 395 100 010 42 1,175 395 100 1, 069 42 1,175 012 162 1,518 27 720 281 100 734 19 535 395 =100 880 21 585 t 30% formaldehyde. I See text iollowing.

Gramsol'oxyalkyl-.

ated compound 1 Obtained in turn from- Percent; whlchds equiv. 50 percent. 1: Oxyalkylcondento grams of .congluconlc. Ex. No. ated desate 1n densate acid to rivative, oxyalkyl- :neutralex. No. v ated deize, grams Conden- Amt.'con- EtO. PrO Solvent rivatlve' Oxyalkyl condensate, densate, amt., amt., amt., ated comsate ex. No. lbs. lbs. lbs. lbs. pound this there was-added 1480 grams of glucomc acid and the trons. ThlS same fact is true in regard to thematerial mnxturezstrrred V1g01'0llSlyfO1'2-h0llIS, and then allowed or materials employed as the' demulslfying agent of my to stand at room temperature for approxlmately 6 hours. process.

A mere trace ofdregs appeared which were withdrawn. The final product was diluted with xylene to give a 50% solution.

The nitrogen basicity aslactually. determined-is somewhat ditferentfrom the nitrogen basicity based on the assumption that all nitroge'natoms, including the. ring nitrogen atoms, are strongly basic. Ordinarily the two ring nitrogen atoms are amino compounds of. the kind described and give a basic effect less than the equivalent of two separate-nitrogen atoms but in theorder of 1.7 nitrogen atoms: In some instances the amount of oxyalkylated product may vary a little from the exact amount stated but, inany .eventthesetwo factors explain. the slight. variation which appearsin respect to the amount of 'gluconic acid used to neutralize the amine condensate. This same factor is'noted in my co-pending application, Serial No..329,486,filed January 2, 1953. p

A number of other examples are included in Table VIII. For convenience, Table VI-Iis'included at this point just preceding Table VIII.

PART 7 Conventional demulsifying agents employed in the treatment of oil field emulsionsf are used as such, or after dilution with any suitable solvent, such as water, petroleum hydrocarbons, such as benzene, toluene, xylene, tar acid-oil, cresol, anthracene-oil, et-c. Alcohols, particularly aliphatic alcohols,such as methyl-alcohol, ethyl alcohol, denatured alcohol, propyl alcohol, "butyl alcohol, hexyl alcohol, octyl alcohol, etc., may be employed as diluents. Miscellaneoussolvents such as .pine oil, carbon etrachloride, sulfur dioxide extract obtained in the refining of petroleum, etc, may be employed as .diluents. Similarly, .the material or .materials employed as the demulsifying agent of my process may be admixed with one-ormore of the solventscustomarily used in connection with conventional. demulsifying agents. Moreover, said material or materials may be used alone or in admixture with other suitable well-known classes of demulsifying agents: 7

It is well known that conventional demulsifying agents may be used in a water-soluble form, or in an oil-soluble form, or in a form exhibiting both oiland water-solubility. Sometimes they may be used in a form which exhibits relatively limited oil-solubility. However, since such re agents are frequently used in a ratio of 1 to 10,000 or 1 to 20,000, or .1 to 30,000,0r even 1 to 40,000,0r1 to 50,000 as indesalting practice, such an apparent insolubility in oiland water is not significant because said reagents undoubtedlyhave solubility within such concentra- Inpracticing the present".process, the treatingordemulsifyin'g-agent' is used in me conventional way, well kn0Wn.-to the art, described, -for example, in Patent 2,626,929fdated January 27, 1953, Part 3, and reference is-made thereto for a de'scr-ipt-ion of conventional p'rocedu'res of demulsify in'g; including batch, continuous, and down-the-hole demuisification, the process essentially involving introducing a small am-ount of demulsifier into a large amount of emulsion with adequate admixture with or without the application or" heat, and allowing the mixture to stratify.

As noted above, the products herein described may be used not only in diluted form, but also may be used ad- *mixed with some other chemicaldemulsifier. A'mixture which illustrates such combination is the following:

Oxyalkylated derivative, for example, the product of Example 1], 20

A cyclohexylamine salt of. a poly'propylated napthalene monosulfonic acid, 24%

Anammonium. saltof .a .polypropylated napthalene mon'osulfonic. acid, 24%;.-

A. sodium. salt of oil-soluble mahogany. petroleum. sulfonic acid, 12%;.

Alhighrboilingaromatic petroleum solvent, 15%;

Isopropyh alcohol, 5%.

The. above proportionsrare all Weight percents.

Having..thus. described my. invent-ion, -.what.iI Iclaim as new and .desire tomiobtaiuby. Letterslate'nt .is:.

1.. A- process for breakingpetroleum-emulsions.of the water-in-oil type characterized by subjecting. the. emulsion to. theaction .ofa demulsifier including .the .gl-uconic'i acid salts of the basic oxyalkylated. productsobtained in turn in the process: o'fcondensing. (a anloxyalkylation-susceptible, fusible, nonsoxygenated organic solvent-soluble, water-insoluble..low-stage;..phenol-aldehyde resin. having an averageamolecular :weight corresponding to .at least 3 and not. over- 6 phenolic .nuclei.:per. resin .molecule;.said

resin being. 1di-functional only: in regard to .methylol-.formingreactivity; said resin :beingderived by reaction between a difunctional monohydricsphenol and an aldehyde. :having not over 8 carbon. atoms and reactive toward said phenol; said. resin being. formed .in ..the. substanti-al. ab sence: of trifunctionalphenols'; saidphenol being; of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) cyclic amidines selected from the class consisting of substituted imidazolines and substituted tetrahydropyrimidines in which there is present at least one basis secondary amino radical and char acterized by freedom from any primary amino radical; and formaldehyde; said condensation reaction being conducted at a temperature sufliciently high to eliminate water and below the pyrolytic point of the react-ants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by an oxyalkylation step by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide.

2. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including the gluconic acid salts of the basic oxyalkylated products obtained in turn in the process of condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over '8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) cyclic amidines selected from the class consisting of substituted imidazolines and substituted tetrahydropyrimidines in which there is present at least one basic secondary amino radical and characterized by freedom from any primary amino radical; and (c) formaldehyde; said condensation reaction be-ing conducted -at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; with the added proviso that the condensation reaction be conducted so as to produce a significant .portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule; and with the further proviso that the resinous condensation product resulting from the process be heatstable and oxyalkylation-susceptible; followed by an oxyalkylation step by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide.

3. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including the gluconic acid salts of the basic oxyalkylated products obtained in turn in the process of condensing (a) an oxyalkylation-sus- 'ceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being d-ifunctional only in regard to methylol-forming reactivity; said resin being difunctional only in regard to mythylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed.

28 in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) cyclic amidines selected from the class consisting of substituted imidazolines and substituted tetrahydropyrimidines in which there is present at least one basic secondary amino radical and characterized by freedom from any primary amino radical; and (0) formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction, with the proviso that the condensation reaction be conducted so as to produce a significant portion ofthe resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom with a resin molecule; and with the further proviso that the resinous condensa tion product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by an oxyalkylation step by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide.

4. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including the gluconic acid salts of the basic oxyalkylated products obtained in turn in the process of condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solventsoluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylolforming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive to ward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 positions; (b) cyclic amidines selected from the class consisting of substituted imidazolines and substituted tetrahydropyrimidines in which there is present at least one basic secondary amino radical and characterized by freedom from any primary amino radical; and (c) formaldehyde; said condensation reaction being conducted at a temperature sufiiciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom of reaction with a resin molecule; with the further proviso that the molar-ratio of reactants be approximately 1,2 and 2 respectively; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by an oxyalkylation step by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) cyclic amidines selected from the class consisting of substituted imidazolines and substituted tetrahydropyrimidines in which there is present at least'one basic secondary amino radical and characterized by freedom from any primary amino radical; and formaldehyde; said condensation reaction being conducted at a temperature sufiiciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction, with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule; by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom of reaction with a resinmolecule; with the added proviso that the molar ratio of reactants be approximately 1,2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by an oxyalkylation step by means of an alphabeta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide,

propylene oxide, butylene oxide, glycide and methylgly-' cide.

6. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including the gluconic acid salts of the basic oxyalkylated products obtained in turn in the process of condensing (a) an 'oxyethylanon-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-formaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per in whichR is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and subsergeant 2',4',6rpsmaa; "(15 eynie amines S's:

lected fromthe class consisting of substituted imida z olines and substituted t'etrahydr'opyrir'nidines in which there is present at least one basic secondar y amino radical and characterized by freedom from any primary amino radical; and ((5) formaldehyde; said condensation reaction being conducted at a temperature sufiicie'ntly high'to eliminate water and below the pyrolytic point of the reactants and resultantsof1reaction, with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom of reaction with a resin molecule; with the added proviso that the molar ratio of reactants be approximately 132 and 2,- respectively; with the further proviso that said procedure involve the use of a solvent; and with the final-proviso thatthe resinous condensation product resulting'from the" process be heat-stable and oxyalkylation-susceptible; followed by an oxyalkylation-step by means of an alpha-beta alkylene oxide having not more than 4 carbonatoms and selected from the class consisting .of ethylene oxide, propylene oxide, butylene oxide,

glycide and methylglycide.

resin 'be'ingdifunctional onlyin regard to methylol-forming reactivity; said resin being'derived by reaction between a difunctional monohydricphenol andformaldehyde; said resin-being-formedin the substantial-absence of trifunct-ional phenols; said phenol being of the formula in which R is an-aliphatic hydrocarbon radical having at least 4 and not more than 14 carbon atoms-and substituted in the 2,4,6 position; (b)' cyclic amidines selected from the class consisting of substituted imidazolin es and substituted tetrahydropyrirnidines in which there is present at least one basic secondary amino radical-and characterized by freedom'from any primary amino radical; and (0) formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water andbelowthe pyrolytic point of the-reactants and resultants of reaction, with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom of reaction with a resin-molecule; with the added provisothat the molar ratio of reactants be approximately 1, 2 and 2, respectively; With the further proviso that said procedure involve the use of a solvent; and with-the final proviso that the resinous condensation product resulting from the process be heat-stableand oxyalkylation-susceptible;- followed by an oxyalkylation step by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide,-glycide and'methylglycide.

, 8. Aprocess -for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action ofa demulsifier including the gluconic acid salts of the basic oxyalkylated products obtained in turn 31 in the process of condensing (a) an oxyethylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-formaldehyde resin having an average molecular weight corresponding to at least 3 and not over phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 14 carbon atoms and substituted in the 2,4,6 position; (b) cyclic amidines selected from the class consisting of substituted imidazolines and substituted tetrahydropyrimidines in which there is present at least one basic secondary amino radical and characterized by freedom from any primary amino radical; and (0) formaldehyde; said condensation reaction being conducted at a temperature above the boiling point of water and below 150 C., with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom of reaction with a resin molecule; with the added proviso that the molar ratio of reactants be approximately 1, 2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by an oxyalkylation step by means of an alphabeta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide.

9. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including the gluconic acid salts of the basic oxyalkylated, products obtained in turn in the process of condensing (a) an oxyethylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-formaldehyde resin having an average molecular weight corresponding to at least in which R is a para-substituted aliphatic hydrocarbon radical having at least 4 and not more than 14 carbon atoms; (b) cyclic amidines selected from the class consisting of substituted imidazolines and substituted tetrahydropyrimidines in which there is present at least one basic secondary amino radical and characterized by freedom from any primary amino radical; and (c) formaldehyde; said condensation reaction being conducted at a temperature above the boiling point of water and below 150 C., with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom of reaction with a resin molecule; with the added proviso that the molar ratio of reactants be approximately 1, 2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heatstable and oxyalkylation-susceptible; followed by an oxyalkylation step by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide. V

10. The process of breaking petroleum emulsions as defined in claim 1 wherein the oxyalkylation step of the manufacturing process is limited to the use of both ethylene oxide and propylene oxide in combination.

11. The process of breaking petroleum emulsions as defined in claim 2 wherein the oxyalkylation step of the manufacturing process is limited to the use of both ethylene oxide and propylene oxide in combination.

12. The process of breaking petroleum emulsions as defined in claim 3 wherein the oxyalkylation step of the manufacturing process is limited to the use of both ethylene oxide and propylene oxide in combination.

13. The process of breaking petroleum emulsions as defined in claim 4 wherein the oxyalkylation step of the manufacturing process is limited to the use of both ethylene oxide and propylene oxide in combination.

14. The process of breaking petroleum emulsions as defined in claim 5 wherein the oxyalkylation step of the manufacturing process is limited to the use of both ethylene oxide and propylene oxide in combination.

15. The process of breaking petroleum emulsions as defined in claim 6 wherein the oxyalkylation step of the manufacturing process is limited to the use of both ethylene oxide and propylene oxide in combination.

16. The process of breaking petroleum emulsions as defined in claim 7 wherein the oxyalkylation step of the manufacturing process is limited to the use of both ethylene oxide and propylene oxide in combination.

17. The process of breaking petroleum emulsions as defined in claim 8 wherein the oxyalkylation step of the manufacturing process is limited to the use of both ethylene oxide and propylene oxide in combination.

18. The process of breaking petroleum emulsions as defined in claim 9 wherein the oxyalkylation step of the manufacturing process is limited to the use of both ethyl- V ene oxide and propylene oxide in combination.

19. The process of claim 1 with the proviso that the hydrophile properties of the gluconic acid salt of the oxyalkylated condensation product in an equal weight of xylene are sufficient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water.

20. The process of claim 2 with the proviso that the hydrophile properties of the gluconic acid salt of the oxyalkylated condensation product in an equal weight of xylene are sufficient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water.

21. The process of claim 3 with the proviso that the hydrophile properties of the gluconic acid salt of the oxyalkylated condensation product in an equal weight of xylene are sufficent to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water.

22. The process of claim 4 with the proviso that the hydrophile properties of the gluconic acid salt of the oxyalkylated condensation product in an equal weight of xylene are sufficient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water.

23. The process of claim 5 with the proviso that the hydrophile properties of the gluconic acid salt of the oxyalkylated condensation product in an equal weight of 33 xylene are sufiicient to produce an emulsion when said xylene solution is shaken vigorously with one to three vol umes of water.

24. The process of claim 6 with the proviso that the hydrophile properties of the gluconic acid salt of the oxyalkylated condensation product in an equal weight of xylene are sufiicient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water.

25. The process of claim 7 with the proviso that the hydrophile properties of the gluconic acid salt of the oxyalkylated condensation product in an equal weight of xylene are sufiicient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water.

26. The process of claim 8 with the proviso that the hydrophile properties of the gluconic acid salt of the oxyalkylated condensation product in an equal weight of xylene are suflicient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water.

27. The process of claim 9 with the proviso that the hydrophile properties of the gluconic acid salt of the oxyalkylated condensation product in an equal weight of xylene are sufiicient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water.

28. The process of claim 10 with the proviso that the hydrophile properties of the gluconic acid salt of the oxyalkylated condensation product in an equal weight of xylene are sufiicient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water.

29. The process of claim 11 with the proviso that the hydrophile properties of the gluconic acid salt of the oxyalkylated condensation product in an equal weight of xylene are sufficient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water.

30. The process of claim 12 with the proviso that the hydrophile properties of the gluconic acid salt of the oxyalkylated condensation product in an equal weight of xylene are sufficient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water.

31. The process of claim 13 with the proviso that the hydrophile properties of the gluconic acid salt of the hydrophile properties of the gluconic acid salt of the oxyalkylated condensation product in an equal Weight of xylene are sufiicient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water.

34. The process of claim 16 with the proviso that the hydrophile properties of the gluconic acid salt of the oxyalkylated condensation product in an equal weight of xylene are sufiicient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water.

35. The process of claim 17 with the proviso that the hydrophile properties of the gluconic acid salt of the oxyalkylated condensation product in an equal weight of xylene are sufiicient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water.

36. The process of claim 18 with the proviso that the hydrophile properties of the gluconic acid salt of the oxyalkylated condensation product in an equal weight of xylene are sufficient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water.

References Cited in the file of this patent UNITED STATES PATENTS 2,031,557 Bruson Feb. 18, 1936 2,451,153 Charlton et a1 Oct. 12, 1948 2,456,357 Allen Dec. 14, 1948 2,499,365 De Groote et a1 Mar. 7, 1950 2,542,001 De Groote et al. Feb. 20, 1951 2,568,739 Kirkpatrick et al. Sept. 25, 1951 2,679,488 De Groote May 25, 1954 2,695,891 De Groote Nov. 30, 1954 

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIER INCLUDING THE GLUCONIC ACID SALTS OF THE BASIC OXYALKYLATED PRODUCTS OBTAINED IN TURN IN THE PROCESS OF CONDENSING (A) AN OXYALKYLATION-SUSCEPTIBLE, FUSIBLE, NON-OXYGENATED ORGANIC SOLVENT-SOLUBLE, WATER-INSOLUBLE, LOW-STAGE PHENOL-SLDEHYDE RESIN HAVING AN AVERAGE MOLECULAR WEIGHT CORRESPONDING TO AT LEAST 3 AND NOT OVER 6 PHENOL NUCLEI PER RESIN MOLECULE; SAID RESIN BEING DIFUNCTIONAL ONLY IN REGARD TO METHYLOL-FORMING REACTIVITY; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONAL PHENOLS; SAID PHENOL BEING OF THE FORMULA 